A. The Fusion Process
The fusion process is one of the basic techniques used in the glass making art to produce sheet glass. See, for example, Varshneya, Arun K., “Flat Glass,” Fundamentals of Inorganic Glasses, Academic Press, Inc., Boston, 1994, Chapter 20, Section 4.2., 534-540. Compared to other processes known in the art, e.g., the float and slot draw processes, the fusion process produces glass sheets whose surfaces have superior flatness and smoothness. As a result, the fusion process has become of particular importance in the production of the glass sheets used in the manufacture of various electronic devices. As just two examples, fusion-produced glass sheets have been used as substrates in the production of flat panel display devices, e.g., liquid crystal displays (LCDs), and as faceplates, e.g., touch screens, in mobile electronic devices.
The fusion process, specifically, the overflow downdraw fusion process, is the subject of commonly-assigned U.S. Pat. Nos. 3,338,696 and 3,682,609, to Stuart M. Dockerty, the contents of which are incorporated herein by reference. A schematic drawing of the process of these patents is shown in FIG. 1. As illustrated therein, the system includes a supply pipe 9 which provides molten glass to a collection trough 11 formed in a free-space spanning, refractory body 13 known as an “isopipe.”
Once steady state operation has been achieved, molten glass passes from the supply pipe to the trough and then overflows the weirs (i.e., the tops of the trough on both sides), thus forming two sheets of glass that flow downward and inward along the outer surfaces of the isopipe. The two sheets meet at the bottom or root 15 of the isopipe, where they fuse together into a single sheet, e.g., a sheet having a thickness of ˜700 microns. The single sheet is then fed to drawing equipment (represented schematically by arrows 17 in FIG. 1), which controls the thickness of the sheet by the rate at which the sheet is drawn away from the root.
As can be seen in FIG. 1, the outer surfaces of the final glass sheet do not contact any part of the outside surface of the isopipe during any part of the process. Rather, these surfaces only see the ambient atmosphere. The inner surfaces of the two half sheets which form the final sheet do contact the isopipe, but those inner surfaces fuse together at the root of the isopipe and thus become the fusion line which is buried in the body of the final sheet. In this way, the superior properties of the outer surfaces of the final sheet are achieved.
B. Isopipe Requirements
As is evident from the foregoing, isopipe 13 is critical to the success of the fusion process as it makes direct contact with the glass during the forming process. Thus, the isopipe needs to fulfill strict mechanical and chemical requirements to have a lifetime that is not too short and to deliver a quality sheet glass product.
With regard to mechanical requirements, during use, a vertical temperature gradient is imposed on the isopipe to manage the viscosity of the molten glass being formed into the glass sheets. In particular, at the root of the isopipe, the glass viscosity typically needs to be in the range of approximately 100 to 300 kP, and to achieve this viscosity the vertical temperature gradient is, for example, on the order of 50-100° C. In addition to this steady-state temperature gradient, the isopipe must also be able to withstand transient gradients during heat-up, as well as during maintenance and repair operations, e.g., during replacement of one or more of the external heating elements used to maintain the pipe at its operating temperature.
In addition to the ability to withstand temperature gradients, an isopipe needs to have a substantially constant configuration at its use temperature. Dimensional stability is of great importance since changes in isopipe geometry affect the overall success of the fusion process. See, for example, Overman, U.S. Pat. No. 3,437,470, and Japanese Patent Publication No. 11-246230. Unfortunately, the conditions under which the isopipe is used make it susceptible to dimensional changes. Thus, the isopipe operates at elevated temperatures on the order of 1000° C. and above. Moreover, the isopipe operates at these elevated temperatures while supporting its own weight as well as the weight of the molten glass overflowing its sides and in trough 11, and at least some tensional force that is transferred back to the isopipe through the fused glass as it is being drawn.
Depending on the width of the glass sheets that are to be produced, the isopipe can have an unsupported length of two meters or more. Current business trends are towards ever larger glass sheets requiring ever larger isopipes for their formation. For an isopipe span on the order of 13 feet, the weight of an isopipe made from zircon (see below) is estimated to be in excess of 15,000 pounds. Moreover, analysis shows that the rate of isopipe sag due to creep (see below) is proportionate to its length raised to the fourth power and inversely proportionate to the square of its height. Accordingly, a doubling in the length of the isopipe (with the same life requirement and temperature capability) requires either a 16 fold decrease in intrinsic creep rate or a four fold increase in height.
In addition to the foregoing mechanical requirements, the isopipe has to meet stringent chemical requirements. In particular, the isopipe should not be rapidly attacked by or be the source of defects in the glass. In terms of commercial production, the defect levels in glass sheets produced by the fusion process have to be extremely low, e.g., on the order of 0.01 defects/pound and below. As the size of the glass sheets has increased, meeting these low defect levels has become ever more challenging, making the need for a chemically stable isopipe even more important.
C. Isopipe Materials
To withstand the above demanding conditions, isopipes 13 have been manufactured from isostatically pressed blocks of refractory material. In particular, isostatically-pressed zircon refractories, such as those sold by St. Gobain-SEFPRO of Louisville, Ky., have been used to form isopipes for the fusion process.
In recent years, efforts have been made to improve the mechanical properties of zircon isopipes. In particular, the creep properties of zircon isopipes have been the subject of intensive research. See, for example, commonly-assigned U.S. Pat. No. 6,974,786 to Helfinstine et al. and PCT Patent Publication No. WO 2006/073841 to Tanner et al., the contents of both of which are incorporated herein by reference.
As known in the art, creep is the permanent change in the physical shape of a refractory or other material as a result of an imparted stress usually at elevated temperature. The creep acts in such a way as to relieve the stress, and is usually attributed to grain boundary sliding or material diffusion. Zircon suffers from creep because at high temperature it decomposes to silica liquid and zirconia, and the presence of silica liquid at grain boundaries increases the creep rate.
An isopipe undergoing creep sags in the middle and deforms the weirs over which the glass flows. When the weirs are no longer straight, the glass flow distribution across the length of the isopipe is disturbed and it becomes more difficult and eventually impossible to manage glass sheet formation, thus ending production. Thus, even though zircon is considered to be a high performance refractory material, in practice, isopipes composed of commercially available zircon exhibit dimensional changes which limit their useful life.
In addition to creep, as disclosed in commonly-assigned U.S. Provisional Application No. 61/363,445 filed on Jul. 12, 2010 and entitled “High Static Fatigue Alumina Isopipes” (hereinafter referred to as the “'445 application”), static fatigue is also a critical property of isopipe materials, both with regard to isopipes in general and alumina isopipes in particular. As indicated above, the present application claims priority from the '445 application and its contents are incorporated herein by reference in their entirety.
As to chemical stability, zircon is known to dissolve into alkali-free glasses (e.g., LCD glasses) at the hotter regions near the weirs of the isopipe and then precipitate in the cooler regions near the root to form secondary zircon crystals. These crystals can be sheared off by the glass flow and become inclusions in the sheet. Secondary crystals incorporated into the drawn glass are visual defects, and finished LCD panels with such defects are rejected. As disclosed in commonly-assigned U.S. Patent Publication No. 2003/0121287, published Jul. 3, 2003, the contents of which are incorporated herein by reference, secondary zircon precipitation can be controlled by restricting the weir-root temperature difference to less than about 100° C.
In accordance with the '445 application, it has been discovered that although zircon isopipes can be used with some alkali-containing glasses, they are incompatible with others. In particular, zircon can develop a blocky morphology and a surface layer composed of zirconia and having a “fish-egg” appearance when exposed to glasses having high levels of alkali (i.e., glasses wherein, on an oxide basis, the sum of Na2O, K2O, and Li2O is greater than or equal to 10 weight percent; hereinafter referred to as “high alkali glasses”). The inability to use zircon isopipes with high alkali glasses is a serious deficiency since the glasses are particularly useful in applications requiring chip and scratch resistant glass surfaces, e.g., touch screens, watch crystals, cover plates, solar concentrators, windows, screens, containers, and the like. See, for example, commonly-assigned U.S. Pat. No. 7,666,511, U.S. Patent Publication No. US 2009/0215607, and U.S. application Ser. No. 12/542,946, filed Aug. 18, 2009, the contents of all of which are incorporated herein by reference.
In addition to zircon, isopipes have also been made of alumina. See, for example, commonly-assigned U.S. Pat. No. 4,018,965, the contents of which are incorporated herein by reference. In particular, besides its zircon refractories, St. Gobain-SEFPRO of Louisville, Ky., has also sold alumina refractories for use as isopipes, specifically, its A1148 alumina refractory.
At first blush, A1148 would appear to be a better material than zircon for use in isopipes since it has a lower creep rate, and in the early days of the fusion process, A1148 was the material of choice. In those days, the isopipes were typically composed of two pieces, i.e., a top portion containing the trough and a lower portion containing the sloping sides, and were generally shorter than modern isopipes. Also, the forming temperatures of the glasses being produced in the early days were lower than those used today, e.g., early applications of the fusion process involved glasses having forming temperatures around 1000° C. or less, e.g., 800-1000° C., while today's glasses are formed on fusion draws at temperatures as high as 1300° C., with 1200-1230° C. being typical. Under the conditions that prevailed in the past, A1148 performed successfully and was routinely used.
However, over time and, in particular, in connection with the growth in popularity of the fusion process as a preferred method for making alkali-free glass substrates for display applications, alumina was phased out and replaced with zircon. Today, most of the display substrates made by the fusion process are made with zircon isopipes. But, as noted above, zircon isopipes are chemically-incompatible with the high alkali glasses which are becoming dominant in the personal (portable) electronics field.
Moreover, as discussed in the '445 application, although historically A1148 alumina was usable as an isopipe material, under modern conditions, A1148 alumina is a poor material and, indeed, is potentially dangerous. Specifically, in accordance with the recognition that static fatigue is a critical parameter for a candidate isopipe material, the static fatigue of A1148 alumina was determined in the '445 application and used to calculate times-to-failure for A1148 under conditions representative of those encountered during the use of an isopipe. That analysis showed that A1148 will fail during use and, in particular, will fail under conditions that cannot be avoided, e.g., during maintenance and repair of the heating elements employed to heat an isopipe. Such a failure can literally cause the isopipe to break into parts thus endangering portions of a fusion machine lying below the isopipe, as well as personnel working in the vicinity of the machine.
D. The Use of Tin in Glass Manufacturing by the Fusion Process
Tin is a common component of glasses made by the fusion process. For many years, tin electrodes have been used to electrically heat molten glass and as the electrodes wear, tin is introduced into the glass. More recently, tin has become a batch component of glasses made by the fusion process. Specifically, in the effort to make “green” glasses, the fining agents arsenic and antimony have been reduced and/or removed from fusion glass and replaced by tin. See commonly-assigned U.S. Pat. Nos. 7,851,394 and 7,534,734.
Accordingly, the formation of tin-containing defects in fusion glasses is a serious problem since to remove tin from the glass would require the development of new electrical heating systems and would eliminate tin as a fining agent for green glasses. As discussed fully below, it has been surprisingly found that alumina isopipes can be a source of tin-containing defects in fusion glasses even when the isopipes have a low tin content which in and of itself would not be expected to lead to tin-containing defects. The mechanism underlying this anomalous behavior is presented below, as well as techniques for ensuring that the tin-containing defect level in fusion glasses is kept within acceptable limits.